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2nd Lecture
CARBOHYDRATE
Structure and functions
Cx(H2O)
y
Hydrated carbon!
I
(CH2O)n or H - C - OH
I
Biochemistry
Carbohydrates
• Many carbohydrates are soluble in water.
• The usual chemical test for the simpler
carbohydrates is heating with Benedict’s
solution.
• The formula for a carbohydrate is
(CH2O)n
• The n represents the number of times the
CH2O unite is repeated.
Biochemistry
Classification of carbohydrates
Monosaccharides (monoses or glycoses)
Trioses, tetroses, pentoses, hexoses
Oligosaccharides
Di, tri, tetra, penta, up to 9 or 10
Most important are the disaccharides
Polysaccharides or glycans
Homopolysaccharides
Heteropolysaccharides
Complex carbohydrates
Biochemistry
Monosaccharides
also known as simple sugars
classified by
1the number of carbons and
2whether aldoses or ketoses
most (99%) are straight chain compounds
D-glyceraldehyde is the simplest of the aldoses
(aldotriose)
all other sugars have the ending ose (glucose,
galactose, ribose, lactose, etc…)
Biochemistry
Aldose sugars
H H H H H
C O C O C O C O C O
(H C OH)n H C OH H C OH H C OH H C OH
CH2OH CH2OH H C OH H C OH H C OH
Ketose sugars
CH2OH CH2OH
CH2OH
CH2OH
C O C O CH2OH
C O
C O
(H C OH)n H C OH C O
H C OH
CH2OH
CH2OH H C OH H C OH
CH2OH
CH2OH H OH
Ketose Ketotriose Ketotetrose
n=1 Ketopentose H C OH
n=0
n=2
CH2OH
Ketohexose
n=3
Biochemistry
CONCEPTS OF ISOMERS
D vs L Designation
D & L designations CHO CHO
are based on the
H C OH HO C H
configuration about
the single asymmetric CH2OH CH2OH
C in glyceraldehyde. D-glyceraldehyde L-glyceraldehyde
The lower
CHO CHO
representations are
Fischer Projections. H C OH HO C H
CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde
Biochemistry
Sugar Nomenclature
For sugars with more O H O H
than one chiral center, C C
D or L refers to the
H – C – OH HO – C – H
asymmetric C farthest
HO – C – H H – C – OH
from the aldehyde or
H – C – OH HO – C – H
keto group.
H – C – OH HO – C – H
Most naturally occurring CH2OH CH2OH
sugars are D isomers. D-glucose L-glucose
Biochemistry
Properties
Differences in structures of sugars are
responsible for variations in properties
Physical
Crystalline form; solubility; rotatory power
Chemical
Reactions (oxidations, reductions, condensations)
Physiological
Nutritive value (human, bacterial); sweetness;
absorption
Biochemistry
anomer anomer
H H
An aldehyde can
react with an
C O + R' OH R' O C OH
alcohol to R R
form a aldehyde alcohol hemiacetal
hemiacetal.
R R
ketone or aldehyde HO
3
C H D-glucose
reacts with a distal H C OH (linear form)
4
OH. H C OH
5
Glucose forms an 6
CH2OH
intra-molecular 6 CH2OH 6 CH2OH
hemiacetal, as the C1 5 O 5 O
H H H OH
aldehyde & C5 OH H H
4 H 1 4 H 1
OH OH
react, to form a 6-
OH OH OH H
member pyranose ring, 3 2 3 2
H OH H OH
named after pyran.
a-D-glucose b-D-glucose
On the same
side as
attacking OH, is
-anomer!
On the opposite
side as
attacking OH, is
-anomer!
Reactions of monosaccharides
Carbonyl reactions:
Osazone formation
Cyanohydrin reaction
Reduction
Oxidation
Action of base
Action of acid
Ring chain tautomerism
Alcohol reactions
Glycoside formation
Ether formation
Ester formation
Biochemistry
Formation of osazones
once used for the identification of sugars
consists of reacting the monosaccharide with
phenylhydrazine
a crystalline compound with a sharp melting point
will be obtained
D-fructose and D-mannose give the same osazone as
D-glucose
seldom used for identification; we now use HPLC or
mass spectrometry
Biochemistry
Biochemistry
Disaccharide Synthesis
Maltose, a cleavage H
5 O H H
5 O H
H H
product of starch 4 OH H 1 4
OH H 1
(e.g., amylose), is a OH O OH
3 2 3 2
disaccharide with an H OH H OH
a(1 4) glycosidic maltose
link between C1 - 6 CH2OH 6 CH2OH
C4 OH of 2 5 O 5 O OH
H H
glucoses. H
1
H
4
OH H O 4
OH H 1
It is the a anomer H H
OH
(C1 O points down). 3 2 3 2
H OH H OH
cellobiose
Sucrose
a-D-glucopyranosido-b-D-fructofuranoside
b-D-fructofuranosido-a-D-glucopyranoside
also known as tablet sugar
commercially obtained from sugar cane or sugar beet
hydrolysis yield glucose and fructose (invert sugar) (
sucrose: +66.5o ; glucose +52.5o; fructose –92o)
used pharmaceutically to make syrups, troches
Biochemistry
Sugar cane
Sugar beet
Biochemistry
Polysaccharides or glycans
homoglycans (starch, cellulose, glycogen, inulin)
heteroglycans (gums, mucopolysaccharides)
characteristics:
polymers (MW from 200,000)
White and amorphous products (glassy)
not sweet
not reducing; do not give the typical aldose or ketose reactions
form colloidal solutions or suspensions
Biochemistry
Starch
most common storage polysaccharide in
plants
composed of 10 – 30% a-amylose and 70-
90% amylopectin depending on the source
the chains are of varying length, having
molecular weights from several thousands to
half a million
Biochemistry
suspensions of amylose
in water adopt a helical
conformation
(in starch)
(in cellulose)
Biochemistry
Cellulose
Polymer of b-D-glucose attached by b(1,4) linkages
Yields glucose upon complete hydrolysis
Partial hydrolysis yields cellobiose
Most abundant of all carbohydrates
Cotton flax: 97-99% cellulose
Wood: ~ 50% cellulose
Gives no color with iodine
Held together with lignin in woody plant tissues
Biochemistry
Structure of cellulose
Biochemistry
Glycogen
also known as animal starch
stored in muscle and liver
present in cells as granules (high MW)
contains both a(1,4) links and a(1,6) branches at
every 8 to 12 glucose unit
complete hydrolysis yields glucose
glycogen and iodine gives a red-violet color
hydrolyzed by both a and b-amylases and by
glycogen phosphorylase
Biochemistry
CH2OH CH2OH
H O O
glycogen
H H H
H H
OH H OH H 1
O
OH
O
H OH H OH
Starches
more branching
Biochemistry
Cellulose
Biochemistry
Sugar derivatives
COOH CHO
CH2OH
H C OH H C OH
H C OH
HO C H HO C H
H C OH
H C OH H C OH
H C OH
H C OH H C OH
CH2OH
CH2OH COOH
D-ribitol
D-gluconic acid D-glucuronic acid
Sugar derivatives
CH2OH CH2OH
H O H H O H
H H
OH H OH H
OH OH OH O OH
H NH2 H N C CH3
H
a-D-glucosamine a-D-N-acetylglucosamine